Chiral reactive mesogen mixture

Abstract

The invention relates to chiral reactive mesogen (RM) mixtures, polymer films obtained thereof, and the use of the mixtures and polymer films in optical, electrooptical or electronic components or devices, in decorative, security or cosmetic applications, especially for use in broadband reflective polarizers.

1. A mixture comprising the following components
 A) from 30 to 80% of component A consisting of one or more compounds of formula I 
 
       
         
           
           
               
               
           
         
         wherein 
         P is a polymerizable group, 
         Sp is a spacer group or a single bond, 
         A 1,2  independently of each other denote 1,4-phenylene or naphthalene-2,6-diyl, wherein one or more CH groups are optionally replaced by N, and which are unsubstituted or substituted by one or more groups L, 
         Z 1,2  are, in case of multiple occurrence each independently of one another, —COO—, —OCO—, —O—COO—, —C≡C— or a single bond, 
         R 1  denotes P-Sp-, F, Cl, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —SF 5 , or straight chain or branched alkyl with 1 to 12 C atoms, wherein one or more CH 2  groups are optionally replaced by —O—, —S—, —CO—, —CS— or NR 0  in such a manner that O and/or S atoms are not directly linked with each other, and wherein one or more H atoms are optionally replaced by F or Cl, 
         L are, in case of multiple occurrence each independently of one another, P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR 0 R 00 , —C(═O)X, —C(═O)OR 0 , —C(═O)R 0 , —NR 0 R 00 , —OH, —SF 5 , optionally substituted silyl, aryl or heteroaryl with 1 to 12 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, 
         X is halogen, 
         R 0  and R 00  are independently of each other H or alkyl with 1 to 12 C atoms, 
         r are each independently of one another 0, 1, 2, 3 or 4, preferably 0 or 1, 
         m1 and m2 are independently of each other 0 or 1, 
         and 
         B) from 5 to 50% of component B consisting of one or more reactive mesogens having two or more polymerizable groups, 
         and 
         C) from 0.2 to 10% of component C consisting of one or more compounds of formula II 
       
       
         
           
           
               
               
           
         
         wherein 
         R 0 * is H or P 0 , 
         P 0  is a polymerizable group, 
         A 0  and B 0  are, in case of multiple occurrence independently of one another, 1,4-phenylene that is unsubstituted or substituted with 1, 2, 3 or 4 groups L, wherein L is as defined above, or trans-1,4-cyclohexylene, 
         X 1  and X 2  are independently of each other —O—, —COO—, —OCO—, —O—CO—O— or a single bond, 
         Z 0  are, in case of multiple occurrence independently of one another, —COO—, —OCO—, —O—CO—O—, —OCH 2 —, —CH 2 O—, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —(CH 2 ) 4 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —C≡C—, —CH═CH—, —CH═CH—COO—, —OCO—CH═CH— or a single bond, 
         t are, independently of each other, 0, 1, 2 or 3, 
         u is 0, 1 or 2, 
         x is 0 or an integer from 1 to 12, 
         z is 0 or 1, 
         and wherein the naphthalene rings can additionally be substituted with one or more identical or different groups L, wherein L is as defined above, 
         and 
         D) 
         from 0.1 to 8% of component D consisting of one or more polymerization initiators; 
         and which mixture has a reflection peak in the visible wavelength range. 
       
     
     
       2. A mixture according to  claim 1 , wherein in that in formula I m1=m2=0 and R 1  is alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms. 
     
     
       3. A mixture according to  claim 1 , wherein the one or more compounds of formula II are of formula IIa 
       
         
           
           
               
               
           
         
       
       wherein A 0 , B 0 , Z 0 , R 0 , u and x have the meanings given for the compound of formula II, and (OCO) denotes —O—CO— or a single bond. 
     
     
       4. A mixture according to  claim 1 , wherein the one or more compounds of component B are of formula IIIa 
       
         
           
           
               
               
           
         
         wherein 
         Z 0 * are, each independently of each other, —COO—, —OCO—, —CH 2 CH 2 —, —CF 2 O—, —OCF 2 —, —CH≡CH—, —CH═CH—, —OCO—CH═CH—, —CH═CH—COO—, or a single bond, 
         P 0  is, each independently of one another, a polymerizable group, 
         L are, in case of multiple occurrence each independently of one another, P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR 0 R 00 , —C(═O)X, —C(═O)OR 0 , —C(═O)R 0 , —NR 0 R 00 , —OH, —SF 5 , optionally substituted silyl, aryl or heteroaryl with 1 to 12 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, 
         r are, each independently of each other, 0, 1, 2, 3 or 4, 
         x and y are independently of each other 0 or identical or different integers from 1 to 12, and 
         z is 0 or 1, with z being 0 if the adjacent x or y is 0. 
       
     
     
       5. A mixture according to  claim 1 , comprising from 3 to 4% of component D. 
     
     
       6. A mixture according to  claim 1 , further comprising a component E consisting of one or more surfactants. 
     
     
       7. A mixture according to  claim 1 , comprising the following components
 a component A, 
 a component B, which optionally comprises one or more compounds of formula IIIa 
 
       
         
           
           
               
               
           
         
         wherein 
         Z 0  are, each independently of each other, —COO—, —OCO—, —CH 2 CH 2 —, —CF 2 O—, —OCF 2 —, —C≡C—, —CH═CH—, —OCO—CH═CH—, —CH═CH—COO—, or a single bond, 
         P 0  is, each independently of one another, a polymerizable group, 
         L are, in case of multiple occurrence each independently of one another, P-Sp-, F, Cl, Br, I, —CN, —NO 2 , —NCO, —NCS, —OCN, —SCN, —C(═O)NR 0 R 00 , —C(═O)X, —C(═O)OR 0 , —C(═O)R 0 , —NR 0 R 00 , —OH, —SF 5 , optionally substituted silyl, aryl or heteroaryl with 1 to 12 C atoms, and straight chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy with 1 to 12 C atoms, wherein one or more H atoms are optionally replaced by F or Cl, 
         r are, each independently of each other, 0, 1, 2, 3 or 4, 
         x and y are independently of each other 0 or identical or different integers from 1 to 12, and 
         z is 0 or 1, with z being 0 if the adjacent x or y is 0, 
         a component C, 
         a component D consisting of one or more polymerization initiators, 
         optionally a component E consisting of one or more surfactants, 
         and one or more of the following components 
         a component F consisting of one or more RMs different from compounds of formula I, II or IIIa, 
         a component G consisting of one or more chain transfer agents, 
         a component H consisting of one or more dyes, and 
         a component I consisting of one or more stabilizers. 
       
     
     
       8. A mixture according to  claim 1 , comprising the following components
 from 0.01 to 5% of compounds of component D, 
 optionally from 0.1 to 2% of compounds of component E consisting of one or more surfactants, 
 optionally from 2 to 30% of compounds of component F consisting of one or more RMs different from compounds of formula I, II or IIIa, 
 optionally from 0.1 to 5% of compounds of component G consisting of one or more chain transfer agents, 
 optionally from 0.1 to 5% of compounds of component H consisting of one or more dyes, and 
 optionally from 0.01 to 0.2 of compounds of component I consisting of one or more stabilizers. 
 
     
     
       9. An anisotropic polymer or polymer film obtainable by polymerizing a mixture according to  claim 1  in its oriented state in form of a thin film or layer. 
     
     
       10. An optical, electrooptical or electronic component or device, or broadband reflective optical polarizer, comprising a mixture according to  claim 1 , or an anisotropic polymer or polymer film obtainable by polymerizing said mixture in its oriented state in form of a thin film or layer. 
     
     
       11. A device or component according to  claim 10 , which is selected from the group consisting of electrooptical displays, LCDs, optical films, polarizers, compensators, beam splitters, reflective films, alignment layers, colour filters, holographic elements, hot stamping foils, coloured images, decorative and security markings, LC pigments, adhesives, non-linear optic (NLO) devices, optical information storage devices, electronic devices, organic semiconductors, organic field effect transistors (OFET), integrated circuits (IC), thin film transistors (TFT), Radio Frequency Identification (RFID) tags, organic light emitting diodes (OLED), organic light emitting transistors (OLET), electroluminescent displays, organic photovoltaic (OPV) devices, organic solar cells (O-SC), organic laser diodes (O-laser), organic integrated circuits (O-IC), lighting devices, sensor devices, electrode materials, photoconductors, photodetectors, electrophotographic recording devices, capacitors, charge injection layers, Schottky diodes, planarizing layers, antistatic films, conducting substrates, conducting patterns, photoconductors, electrophotographic applications, electrophotographic recording, organic memory devices, biosensors, biochips, optoelectronic devices requiring similar phase shift at multiple wavelengths, combined CD/DVD/HD-DVD/Blu-Rays, reading, writing, re-writing data storage systems, and cameras. 
     
     
       12. A mixture according to  claim 7 , wherein component B comprises one or more compounds of formula IIIa. 
     
     
       13. A mixture according to  claim 7 , wherein the one or more compounds of formula II are of formula IIa 
       
         
           
           
               
               
           
         
       
       wherein A 0 , B 0 , Z 0 , R 0 , u and x have the meanings given for the compound of formula II, and (OCO) denotes —O—CO— or a single bond. 
     
     
       14. A mixture according to  claim 1 , wherein P 0  is an acryl, methacryl, oxetane, epoxy, vinyl, vinyloxy, propenyl ether or styrene group. 
     
     
       15. A mixture according to  claim 1 , wherein the one or more compounds of formula I are of formula Ia: 
       
         
           
           
               
               
           
         
       
       wherein P, Sp and R 1  have the meanings given for the compound of formula I, and r1, r2 and r3 are independently of each other 0, 1, 2, 3 or 4. 
     
     
       16. A mixture according to  claim 15 , wherein r2 is different from 0, and r1 and/or r3 are 0. 
     
     
       17. A mixture according to  claim 1 , comprising the following components
 from 40 to 70% of compounds of component A, 
 from 20 to 40% of compounds of component B, 
 from 2 to 5% of compounds of component C, 
 from 0.02 to 5% of compounds of component D, 
 optionally from 0.1 to 2% of compounds of component E consisting of one or more surfactants, 
 optionally from 2 to 30% of compounds of component F consisting of one or more RMs different from compounds of formula I, II or IIIa, 
 optionally from 0.1 to 5% of compounds of component G consisting of one or more chain transfer agents, 
 optionally from 0.1 to 5% of compounds of component H consisting of one or more dyes, and 
 optionally from 0.01 to 0.2 of compounds of component I consisting of one or more stabilizers. 
 
     
     
       18. A mixture according to  claim 1 , wherein component B comprises one or more compounds of formula I wherein R 1  is P-Sp. 
     
     
       19. A mixture according to  claim 1 , comprising from 40 to 70% of compounds of component A. 
     
     
       20. A mixture according to  claim 1 , which has a bandwidth Δλ of the reflected wavelength band at half height of between 115 to 335 nm.